Solar cell and method for manufacturing the same

ABSTRACT

Disclosed is a solar cell including a first electrode, a second electrode, and a first conversion layer disposed therebetween. The first electrode is closer to a light incident side than the second electrode. The first conversion layer is a composition-gradient perovskite. A part of the first conversion layer adjacent to the first electrode has an energy gap less than that of a part of the first conversion layer adjacent to the second electrode.

CROSS REFERENCE TO RELATED APPLICATIONS

The application is based on, and claims priority from, Taiwan Application Serial Number 103143429, filed on Dec. 12, 2014, and claims the benefit of U.S. Provisional Application No. 62/025,180, filed on Jul. 16, 2014, the disclosure of which is hereby incorporated by reference herein in its entirety.

TECHNICAL FIELD

The technical field relates to a perovskite conversion layer of a solar cell, and in particular it relates to a composition-gradient perovskite layer and method for manufacturing the same.

BACKGROUND

Organic metal perovskite materials are potential materials for solar cells due to their excellent physical properties. Organic lead halide perovskite has a higher efficiency over other perovskite materials. The major conventional method for forming a perovskite layer is coating. For example, two precursors of the perovskite are dissolved in an organic solvent (e.g. DMF), and then spin-coated on an electrode. Alternatively, lead halide (PbX₂) can be dissolved in an organic solvent and spin-coated to form a PbX₂ film on an electrode, and the PbX₂ film is then dipped in methylammonium iodide (MAI) to form a perovskite film of Pb(CH₃NH₃)X₂I. However, the solvent in the next coating step may dissolve the previously formed perovskite film formed previously. Even if the compositions in each of the coating processes are different, the solvent in different coating processes may dissolve the different compositions in previous coating processes. In short, the general coating processes cannot form a composition-gradient perovskite layer.

Accordingly, a novel method for manufacturing a composition-gradient perovskite layer is called-for.

SUMMARY

One embodiment of the disclosure provides a solar cell, comprising: a first electrode; a second electrode; and a first conversion layer disposed between the first electrode and the second electrode, and the first electrode being closer to a light incident side than the second electrode, wherein the first conversion layer is a composition-gradient perovskite, a part of the first conversion layer adjacent to the first electrode has an energy gap lower than that of a part of the first conversion layer adjacent to the second electrode, and the first conversion layer has a composition of M¹ _(m)M² _((1−m))A[X¹ _(x)X² _((1−x))]₃, wherein each of M¹ and M² is independently a divalent cation of Ge, Sn, or Pb, wherein A is a monovalent cation of methylammonium, ethylammonium, or formamidinium, wherein each of X¹ and X² is independently a monovalent anion of halogen, wherein M¹ has a lower atomic number than M², X¹ has a higher atomic number than X², or a combination thereof; wherein 1≧m≧0, 1≧x≧0, and the m and x are greater at a location that is closer to the first electrode.

One embodiment of the disclosure provides a method of manufacturing a solar cell, comprising: providing m parts by mole of M¹X¹ ₂ by a first deposition source, providing 1−m parts by mole of M²X² ₂ by a second deposition source, and providing a fixed amount of a fixed amount of AX¹ _(t)X² _((1−t)) by a third deposition source to deposit a first conversion layer on a first electrode, wherein the first conversion layer is a composition-gradient perovskite; and forming a second electrode on the first conversion layer, wherein a part of the first conversion layer adjacent to the first electrode has an energy gap lower than that of a part of the first conversion layer adjacent to the second electrode, wherein the first conversion layer has a composition of M¹ _(m)M² _((1−m))AX¹ _((2m+t))X² _((3−2m−t)), m is decreased with a longer deposition time, t is decreased with a longer deposition time, 1≧m≧0, and 1≧t≧0; wherein each of M¹ and M² is independently a divalent cation of Ge, Sn, or Pb, wherein A is a monovalent cation of methylammonium, ethylammonium, or formamidinium, wherein each of X¹ and X² is independently a monovalent anion of halogen, wherein M¹ has a lower atomic number than M², X¹ has a higher atomic number than X², or a combination thereof.

One embodiment of the disclosure provides a method of manufacturing a solar cell, comprising: providing m parts by mole of M¹X¹ ₂ by a first deposition source and providing 1−m parts by mole of M²X² ₂ by a second deposition source to deposit a M¹ _(m)M² _((1−m))X¹ _(2m)X² _((2−2m)) layer on a first electrode; providing AX¹ or AX² by a third deposition source, such that AX¹ or AX² reacts with the M¹ _(m)M² _((1−m))X¹ _(2m)X² _((2−2m)); and layer to form a first conversion layer on the first electrode, wherein the first conversion layer is a composition-gradient perovskite of M¹ _(m)M² _((1−m))AX¹ _((2m+1))X² _((2−2m)) or M¹ _(m)M² _((1−m))AX¹ _((2m))X² _((3−2m)); and forming a second electrode on the first conversion layer, wherein a part of the first conversion layer adjacent to the first electrode has an energy gap lower than that of a part of the first conversion layer adjacent to the second electrode, wherein m is decreased with a longer deposition time and 1≧m≧0; wherein each of M¹ and M² is independently a divalent cation of Ge, Sn, or Pb, wherein A is a monovalent cation of methylammonium, ethylammonium, or formamidinium, wherein each of X¹ and X² is independently a monovalent anion of halogen, wherein M¹ has a lower atomic number than M², X¹ has a higher atomic number than X², or a combination thereof.

A detailed description is given in the following embodiments with reference to the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

The disclosure can be more fully understood by reading the subsequent detailed description and examples with references made to the accompanying drawings, wherein:

FIG. 1 shows the deposition of the conversion layer in one embodiment of the disclosure;

FIGS. 2A and 2B show lines of concentration versus deposition time of M¹X¹ ₂, M²X² ₂, and AX¹ _(t)X² _((1−t)) in the deposition chamber of embodiments in the disclosure;

FIG. 3 shows a solar cell in one embodiment of the disclosure;

FIGS. 4A, 4B, 4C, 4D, and 4E show lines of energy gap versus thickness of conversion layers in embodiments of the disclosure;

FIG. 5 shows a solar cell in one embodiment of the disclosure;

FIG. 6 shows the deposition of the conversion layer in one embodiment of the disclosure;

FIGS. 7A and 7B show lines of energy gap versus thickness of conversion layers in embodiments of the disclosure; and

FIGS. 8A, 8B, and 8C show lines of energy gap versus thickness of conversion layers in embodiments of the disclosure.

DETAILED DESCRIPTION

In the following detailed description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the disclosed embodiments. It will be apparent, however, that one or more embodiments may be practiced without these specific details. In other instances, well-known structures and devices are shown schematically in order to simplify the drawing.

One embodiment of the disclosure provides a method for manufacturing a solar cell. As shown in FIG. 1, m parts by mole of M¹X¹ ₂ is provided by a deposition source 11, 1−m parts by mole of M²X² ₂ is provided by a deposition source 13, and a fixed amount of a fixed amount of AX¹ _(t)X² _((1−t)) is provided by a deposition source 15, thereby depositing a conversion layer 17 on a first electrode 19, wherein the conversion layer is a composition-gradient perovskite. FIGS. 2A and 2B show concentrations of M¹X¹ ₂, M²X² ₂, and AX¹ _(t)X² _((1−t)) at different deposition times in the deposition chamber of embodiments in the disclosure. Note that although only 1 part by mole of M¹X¹ ₂ reacts with AX¹ to form M¹AX¹ ₃ at start in FIGS. 2A and 2B, M¹X¹ ₂, M²X² ₂, and AX¹ _(t)X² _((1-t)) may react to form M¹ _(m)M² _((1−m))AX¹ _(2m+t)X² _(3−2m−t) at the start. In short, deposition can be started at time point T in FIGS. 2A and 2B rather than at time point 0. While the deposition time is increased, the m and t are decreased, 1≧m≧0, and M¹ _(m)M² _((1−m))AX¹ _(2m+t)X² _(3−2m−t) can be represented as M¹ _(m)M² _((1−m))A[X¹ _(x)X² _((1−x))]₃, wherein x=(2m+t)/3, and m and x are greater at a location that is closer to the electrode 19. Each of M¹ and M² is independently a divalent cation of Ge, Sn, or Pb. A is a monovalent cation of methylammonium, ethylammonium, or formamidinium. Each of X¹ and X² is independently a monovalent anion of halogen. M¹ has a lower atomic number than M², X¹ has a higher atomic number than X², or a combination thereof.

Subsequently, an electrode 31 can be formed on the conversion layer 17, as shown in FIG. 3. In one embodiment, the electrode 19 is an electrode of a light-incident side, and its composition should be transparent and electrically conductive such as fluorine doped tin oxide (FTO), indium tin oxide (ITO), zinc tin oxide (ZTO), or the like. The electrode 31 can be a general electrical conductor such as carbon material (e.g. active carbon or graphene) or metal (e.g. gold, silver, copper, aluminum, another electrically conductive metal, or an alloy thereof). In one embodiment, a metal oxide semiconductor material (e.g. titanium oxide, zinc oxide, nickel oxide, or tungsten oxide) can be disposed between the electrode 19 and the conversion layer 17 to serve as an electron transport layer. In another embodiment of the disclosure, a hole transport material such as Spiro-OMeTAD, P3HT, CuSCN, CuI, or PEDOT:PSS can be disposed between the electrode 31 and the conversion layer 17 to serve as a hole transport layer.

The composition-gradient conversion layer 17 formed in FIG. 2A has an energy gap diagram as shown in FIG. 4A, and the composition-gradient conversion layer 17 has an energy gap diagram as shown in FIG. 4B. It should be understood that the composition-gradient conversion layer 17, with a part adjacent to the electrode 19 having an energy gap lower than that of a part adjacent to the electrode 31, can be formed by the above processes. In addition, the energy gap of the conversion layer 17 may have other designs as shown in FIG. 4C, 4D, or 4E.

In one embodiment, the M¹X¹ ₂ provided by the deposition source 11 in FIG. 1 is SnI₂, the M²X² ₂ provided by the deposition source 13 in FIG. 1 is PbI₂, and the AX¹ _(t)X² _((1−t)) provided by the deposition source 15 was (CH₃NH₃)I. As such, a part of the conversion layer 17 adjacent to the electrode 19 can be Sn(CH₃NH₃)I₃ with an energy gap of 1.1 eV, a part of the conversion layer 17 adjacent to the electrode 31 can be Pb(CH₃NH₃)I₃ with an energy gap of 1.5 eV, and the composition between the electrodes 19 and 31 can be Sn_(m)Pb_((1−m))(CH₃NH₃)I₃.

In one embodiment, the M¹X¹ ₂ provided by the deposition source 11 in FIG. 1 is PbI₂, the M²X² ₂ A provided by the deposition source 13 in FIG. 1 is PbBr₂, and the AX¹ _(t)X² _((1−t)) provided by the deposition source 15 was (CH₃NH₃)I_(t)Br_((1−t)). As such, a part of the conversion layer 17 adjacent to the electrode 19 can be Pb(CH₃NH₃)I₃ with an energy gap of 1.5 eV, a part of the conversion layer 17 adjacent to the electrode 31 can be Pb(CH₃NH₃)Br₃ with an energy gap of 2.3 eV, and the composition between the electrodes 19 and 31 can be Pb(CH₃NH₃)[I_(x)Br_((1−x))]₃.

The deposition sources 11, 13, and 15 can be sputtering sources or evaporation sources. If the sputtering sources are selected, the ratio of M¹X¹ ₂ and M²X² ₂ can be fine-tuned by controlling the energy bombarding the target. If the evaporation sources are selected, the ratio of M¹X¹ ₂ and M²X² ₂ can be fine-tuned by controlling the temperature of the evaporation sources. In addition, the ratio of X¹ and X² in AX¹ _(t)X² _((1−t)) can be fine-tuned by controlling the flow rate of the halogen gas reacting with A.

In another embodiment of the disclosure, a conversion layer 18 can be deposited on the electrode 19 before depositing the conversion layer 17 on the electrode 19. As shown in FIG. 5, the conversion layer 18 is disposed between the electrode 19 and the conversion layer 17. A part of the conversion layer 18 adjacent to the electrode 19 has an energy gap higher than that of a part of the conversion layer 18 adjacent to the conversion layer 17, a part of the conversion layer 18 adjacent to the conversion layer 17 has an energy gap equal to that of a part of the conversion layer 17 adjacent to the conversion layer 18, and a part of the conversion layer 18 adjacent to the electrode 19 has an energy gap lower than that of a part of the conversion layer 17 adjacent to the electrode 31.

In one embodiment, the step of depositing the conversion layer 18 is described as below. m′ parts by mole of M³X³ ₂ is provided by a deposition source 61, 1−m′ parts by mole of M⁴X⁴ ₂ is provided by a deposition source 63, and a fixed amount of AX³ _(t′)X⁴ _((1−t′)) is provided by a deposition source 65 to deposit the conversion layer 18 on the electrode 19, as shown in FIG. 6. The conversion layer 18 has a composition of M³ _(m′)M⁴ _((1−m′))AX³ _((2m′+t′))X⁴ _((3−2m′−t′)), m is decreased with a longer deposition time, t is decreased with a longer deposition time, 1≧m′≧0, and 1≧t′≧0. M³ _(m)·M⁴ _((1−m′))AX³ _((2m′+t′))X⁴ _((3−2m−t′)) can be represented as M³ _(m′)M⁴ _((1−m′))A[X³ _(x′)X_((1−x′)) ⁴]₃, wherein x′=(2m′+t′)/3, and m′ and x′ are greater at a location that is closer to the electrode 19. Each of M³ and M⁴ is independently a divalent cation of Ge, Sn, or Pb, A is a monovalent cation of methylammonium, ethylammonium, or formamidinium, and each of X³ and X⁴ is independently a monovalent anion of halogen. M³ has a higher atomic number than M⁴, X³ has a lower atomic number than X⁴, or a combination thereof.

The deposition sources 61, 63, and 65 can be sputtering sources or evaporation sources. If the sputtering sources are selected, the ratio of M³X³ ₂ and M⁴X⁴ ₂ can be fine-fine-tuned by controlling the energy bombarding the target. If the evaporation sources are selected, the ratio of M³X³ ₂ and M⁴X⁴ ₂ can be fine-tuned by controlling the temperature of the evaporation sources. In addition, the ratio of X³ and X⁴ in AX³ _(t)X⁴ _((1−t)) can be fine-tuned by controlling the flow rate of the halogen gas reacting with A.

In one embodiment of the disclosure, the composition of a part of the conversion layer 18 adjacent the electrode 19 is gradually changed from Pb(CH₃NH₃)[I_(x)Br_((1−x))]₃ (0<x<1) to Pb(CH₃NH₃)I₃, and the composition of the conversion layer 17 is gradually changed from Pb(CH₃NH₃)I₃ (the interface between the conversion layers 17 and 18) to Pb(CH₃NH₃)Br₃. In another embodiment, the composition of a part of the conversion layer 18 adjacent the electrode 19 is gradually changed from Sn_(m)Pb_((1−m))(CH₃NH₃)I₃ (0<m<1) to Sn(CH₃NH₃)I₃, and the composition of the conversion layer 17 is gradually changed from Sn(CH₃NH₃)I₃ (the interface between the conversion layers 17 and 18) to Pb(CH₃NH₃)I₃.

For example, the conversion layers 18 and 17 may have energy gap diagrams as shown in FIG. 7A or 7B. Note that the energy gap diagram of the conversion layers 18 and 17 can be fine-tuned with other changes in FIGS. 4B to 4E.

In another embodiment, m parts by mole of M¹X¹ ₂ is provided by a deposition source 11 and 1−m parts by mole of M²X² ₂ is provided by a deposition source 13 to deposit a M¹ _(m)M² _((1−m))X¹ _(2m)X² _((2−2m)) layer on an electrode 19. Thereafter, AX¹ or AX² is provided by a deposition source 15, such that AX¹ or AX² reacts with the M¹ _(m)M² _((1−m))X¹ _(2m)X² _((2−2m)) layer to form a conversion layer 17 on the electrode 19, wherein the conversion layer 17 is a composition-gradient perovskite of M¹ _(m)M² _((1−m))AX¹ _((2m+1))X² _((2−2m)) or M¹ _(m)M² _((1−m))AX¹ _((2m))X² _((3−2m)). An electrode 31 is then formed on the conversion layer 17, as shown in FIG. 3. M¹ _(m)M² _((1−m))AX¹ _((2m+1))X² _((2−2m)) can be represented as M¹ _(m)M² _((1−m))A[X¹ _(x)X² _((1−x))]₃, wherein x=(2m+1)/3, and m and x are greater at a location that is closer to the electrode 19. M¹ _(m)M² _((1−m))AX¹ _((2m))X² _((3−m)) can be represented as M¹ _(m)M² _((1−m))A[X¹ _(x)X² _((1−x))]₃, wherein x=2m/3, and m and x are greater at a location that is closer to the electrode 19.

A part of the conversion layer 17 adjacent to the electrode 19 has an energy gap lower than that of a part of the conversion layer 17 adjacent to the electrode 31. In the above deposition, m is decreased with a longer deposition time and 1≧m≧0. Each of M¹ and M² is independently a divalent cation of Ge, Sn, or Pb. A is a monovalent cation of methylammonium, ethylammonium, or formamidinium. Each of X¹ and X² is independently a monovalent anion of halogen. In the composition of the conversion layer 17, M¹ has a lower atomic number than M², X¹ has a higher atomic number than X², or a combination thereof.

Compared to above embodiments, this embodiment is different due to the M¹ _(m)M² _((1−m))AX¹ _((2m))X² _((2−2m)) is pre-formed and AX¹ or AX² are then provided to react with M¹ _(m)M² _((1−m))AX¹ _((2m))X² _((2−2m)) to form the conversion layer, rather than the M¹X¹, M²X², and AX¹ (or AX²) are simultaneously provided and reacted to directly from the conversion layer. The composition and the energy gap diagram of the conversion layer 17 in this embodiment are similar to that in the above embodiments and omitted here.

Similar to the above embodiments, a composition-gradient conversion layer 18 can be further deposited on the electrode 19 before depositing the conversion layer 17 in this embodiment. In other words, the conversion layer 18 is disposed between the conversion layer 17 and the electrode 19. A part of the conversion layer 18 adjacent to the electrode 19 has an energy gap higher than that of a part of the conversion layer 18 adjacent to the conversion layer 17, a part of the conversion layer 18 adjacent to the conversion layer 17 has an energy gap equal to that of a part of the conversion layer 17 adjacent to the conversion layer 18, and a part of the conversion layer 18 adjacent to the electrode 19 has an energy gap lower than that of a part of the conversion layer 17 adjacent to the electrode 31. For example, the energy gap of the conversion layers 18 and 17 can be referred to FIGS. 7A and 7B.

In one embodiment, the step of depositing the conversion layer is described as below. m′ parts by mole of M³X³ ₂ is provided by the deposition source 61 and 1−m′ parts by mole of M⁴X⁴ ₂ is provided by the deposition source 63 to deposit a M³ _(m′)M⁴ _((1−m′))X³ _(2m′)X⁴ _((2−2m′)) layer on the electrode 19. AX³ or AX⁴ is then provided by the deposition source 65, such that AX³ or AX⁴ reacts with the M³ _(m′)M⁴ _((1−m′))X³ _(2m′)X⁴ _((2−2m)) layer to form a conversion layer 18 on the electrode 19, wherein the conversion layer 18 is a composition-gradient perovskite of M³ _(m′)M⁴ _((1−m′))AX³ _((2m′+1))X⁴ _((2−2m′)) or M³ _(m′)M⁴ _((1−m)′)AX³ _((2m′))X⁴ _((3−2m′)). M³ _(m′)M⁴ _((1−m′))AX³ _((2m′+1))X⁴ _((2−2m′)) can be represented as M³ _(m′)M⁴ _((1−m′))A[X³ _(x′)X⁴ _((1−x′))]₃, wherein x′=(2m′+1)/3, and m′ and x′ are greater at a location that is closer to the electrode 19. M³ _(m′)M⁴ _((1−m′))AX³ _((2m′))X⁴ _((3−2m′)) can be represented as M³ _(m′)M⁴ _((1−m′))A[X³ _(x′)X⁴ _((1−x′))]₃, wherein x′=(2m′)/3, and m′ and x′ are greater at a location that is closer to the electrode 19. m′ is decreased with a longer deposition time and 1≧m′≧0. Each of M³ and M⁴ is independently a divalent cation of Ge, Sn, or Pb, A is a monovalent cation of methylammonium, ethylammonium, or formamidinium, and each of X³ and X⁴ is independently a monovalent anion of halogen. In the composition of the conversion layer 18, M³ has a higher atomic number than M⁴, X³ has a lower atomic number than X⁴, or a combination thereof.

Compared to conventional skills, the processes of manufacturing the perovskite conversion layers in the disclosure are free of solvent. As such, the different perovskite compositions in different layers will not be dissolved and mixed by solvent. In other words, the method of the disclosure may control the perovskite composition in different thicknesses of the conversion layer, thereby tuning the energy gap of the conversion layer to improve the conversion efficiency of the solar cell.

Below, exemplary embodiments will be described in detail with reference to the accompanying drawings so as to be easily realized by a person having ordinary knowledge in the art. The inventive concept may be embodied in various forms without being limited to the exemplary embodiments set forth herein. Descriptions of well-known parts are omitted for clarity, and like reference numerals refer to like elements throughout.

EXAMPLES Comparative Example 1

In FIG. 3, the electrode 19 was a TiO₂ layer with a thickness of 90 nm, the electrode 31 was a thin gold film, the conversion layer 17 was a Pb(CH₃NH₃)I₃ layer with a thickness of 400 nm, and a hole transport layer (not shown) between the conversion layer 17 and the electrode 31 was a Spiro-OMeTAD layer with a thickness of 400 nm. The properties of the above solar cell were simulated and calculated by Analysis of Microelectronic and Photonic Structures 1D (AMPS-1D) as described below. The solar cell had an open-circuit voltage of 1.272V, a short-circuit current of 21.683 mA/cm², a filling factor of 0.826, and a conversion efficiency of 22.722%.

Comparative Example 2

In FIG. 3, the electrode 19 was a TiO₂ layer with a thickness of 90 nm, the electrode 31 was a thin gold film, and the conversion layer 17 was a Pb(CH₃NH₃)I₃ layer with a thickness of 400 nm. The properties of the above solar cell were simulated and calculated by AMPS-1D as described below. The solar cell had an open-circuit voltage of 0.838V, a short-circuit current of 17.945 mA/cm², a filling factor of 0.804, and a conversion efficiency of 12.095%.

Example 1

In FIG. 3, the electrode 19 was a TiO₂ layer with a thickness of 90 nm, the electrode 31 was a thin gold film, a part of the conversion layer 17 adjacent to the electrode 19 was Pb(CH₃NH₃)I₃ with a thickness of 300 nm, and a composition-gradient part of the conversion layer 17 was Pb(CH₃NH₃)[I_(x)Br_((1−x))]₃ with a thickness of 100 nm extending from Pb(CH₃NH₃)I₃ to Pb(CH₃NH₃)Br₃. The conversion layer 17 had an energy gap diagram as shown in FIG. 8A. The properties of the above solar cell were simulated and calculated by AMPS-1D as described below. The solar cell had an open-circuit voltage of 1.284V, a short-circuit current of 21.136 mA/cm², a filling factor of 0.840, and a conversion efficiency of 22.807%.

Example 2

In FIG. 3, the electrode 19 was a TiO₂ layer with a thickness of 90 nm, the electrode 31 was a thin gold film, and the conversion layer 17 was divided to three regions from the electrode 19 to the electrode 31: (1) a composition-gradient part of Pb(CH₃NH₃)[I_(x)Br_((1−x))]₃ with a thickness of about 50 nm gradually changed to Pb(CH₃NH₃)I₃, wherein the Pb(CH₃NH₃)[I_(x)Br_((1−x))]₃ had an energy gap that gradually changed from 1.5 eV (or 1.6 eV, 1.8 eV, 2.0 eV, 2.3 eV) to 1.5 eV; (2) a part of Pb(CH₃NH₃)I with a thickness of about 300 nm, wherein the Pb(CH₃NH₃)I had an energy gap of 1.5 eV; and (3) a composition-gradient part of Pb(CH₃NH₃)[I_(x)Br_((1−x))]₃ with a thickness of about 50 nm gradually changed to Pb(CH₃NH₃)Br₃, wherein the Pb(CH₃NH₃)[I_(x)Br_((1−x))]₃ had an energy gap that gradually changed from 1.5 eV to 2.3 eV. The conversion layer 17 had an energy gap diagram as shown in FIG. 8B. The properties of the above solar cells, e.g. an open-circuit voltage, a short-circuit current, a filling factor, and a conversion efficiency, were simulated and calculated by AMPS-1D and tabulated in Table 1.

TABLE 1 The energy gap of the Open- Short- Conver- part of the conversion circuit circuit sion layer 17 adjacent to voltage current Filling efficien- the electrode 19 (Eg) (V) (mA/cm²) factor cy (%) 1.5 1.278 21.448 0.839 23 1.6 1.283 21.393 0.84 23.051 1.8 1.284 21.217 0.839 22.863 2.0 1.289 21.187 0.673 18.399 2.3 1.566 21.162 0.256 8.439

Example 3

In FIG. 3, the electrode 19 was a TiO₂ layer with a thickness of 90 nm, the electrode 31 was a thin gold film, and the conversion layer 17 was divided to three regions from the electrode 19 to the electrode 31: (1) a composition-gradient part of Pb(CH₃NH₃)[I_(x)Br_((1−x))]₃ with a thickness of about 50 nm (or 100 nm, 200 nm, 300 nm, 350 nm) gradually changed to Pb(CH₃NH₃)I₃, wherein the Pb(CH₃NH₃)[I_(x)Br_((1−x))]₃ had an energy gap that gradually changed from 1.6 eV to 1.5 eV; (2) a part of Pb(CH₃NH₃)I with a thickness of about 300 nm (or 250 nm, 150 nm, 50 nm, 0 nm), wherein the Pb(CH₃NH₃)I had an energy gap of 1.5 eV; and (3) a composition-gradient part of Pb(CH₃NH₃)[I_(x)Br_((1−x))]₃ with a thickness of about 50 nm gradually changed to Pb(CH₃NH₃)Br₃, wherein the Pb(CH₃NH₃)[I_(x)Br_((1−x))]₃ had an energy gap that gradually changed from 1.5 eV to 2.3 eV. The conversion layer 17 had an energy gap diagram as shown in FIG. 8C. The properties of the above solar cells, e.g. an open-circuit voltage, a short-circuit current, a filling factor, and a conversion efficiency, were simulated and calculated by AMPS-1D and tabulated in Table 2.

TABLE 2 The thickness The thickness Open- Short- Conver- of region (1) of of region (2) of circuit circuit sion the conversion the conversion voltage current Filling efficien- layer 17 (nm) layer 17 (nm) (V) (mA/cm²) factor cy (%) 50 300 1.283 21.393 0.84 23.051 100 250 1.289 21.336 0.84 23.113 200 150 1.304 21.222 0.841 23.289 300 50 1.327 21.101 0.842 23.582 350 0 1.344 21.034 0.843 23.830

It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed methods and materials. It is intended that the specification and examples be considered as exemplary only, with a true scope of the disclosure being indicated by the following claims and their equivalents. 

What is claimed is:
 1. A solar cell, comprising: a first electrode; a second electrode; and a first conversion layer disposed between the first electrode and the second electrode, and the first electrode being closer to a light incident side than the second electrode, wherein the first conversion layer is a composition-gradient perovskite, a part of the first conversion layer adjacent to the first electrode has an energy gap lower than that of a part of the first conversion layer adjacent to the second electrode, and the first conversion layer has a composition of M¹ _(m)M² _((1−m))A[X¹ _(x)X² _((1−x))]₃, wherein each of M¹ and M² is independently a divalent cation of Ge, Sn, or Pb, wherein A is a monovalent cation of methylammonium, ethylammonium, or formamidinium, wherein each of X¹ and X² is independently a monovalent anion of halogen, wherein M¹ has a lower atomic number than M², X¹ has a higher atomic number than X², or a combination thereof; wherein 1≧m≧0, 1≧x≧0, and the m and x are greater at a location that is closer to the first electrode.
 2. The solar cell as claimed in claim 1, further comprising a second conversion layer disposed between the first conversion layer and the first electrode, wherein the second conversion layer is a composition-gradient perovskite, a part of the second conversion layer adjacent to the first electrode has an energy gap higher than that of a part of the second conversion layer adjacent to the first conversion layer, a part of the second conversion layer adjacent to the first conversion layer has an energy gap equal to that of a part of the first conversion layer adjacent to the second conversion layer, and a part of the second conversion layer adjacent to the first electrode has an energy gap lower than that of a part of the first conversion layer adjacent to the second electrode.
 3. The solar cell as claimed in claim 2, wherein the second conversion layer has a composition of M³ _(m′)M⁴ _((1−m′))A[X³ _(x′)X⁴ _((1−x′))]₃, wherein each of M³ and M⁴ is independently a divalent cation of Ge, Sn, or Pb, wherein A is a monovalent cation of methylammonium, ethylammonium, or formamidinium, wherein each of X³ and X⁴ is independently a monovalent anion of halogen, wherein M³ has a higher atomic number than M⁴, X³ has a lower atomic number than X⁴, or a combination thereof; wherein 1≧m′≧0, 1≧x′≧0, and the m and x are greater at a location that is closer to the first electrode.
 4. A method of manufacturing a solar cell, comprising: providing m parts by mole of M¹X¹ ₂ by a first deposition source, providing 1−m parts by mole of M²X² ₂ by a second deposition source, and providing a fixed amount of a fixed amount of AX¹ _(t)X² _((1−t)) by a third deposition source to deposit a first conversion layer on a first electrode, wherein the first conversion layer is a composition-gradient perovskite; and forming a second electrode on the first conversion layer, wherein a part of the first conversion layer adjacent to the first electrode has an energy gap lower than that of a part of the first conversion layer adjacent to the second electrode, wherein the first conversion layer has a composition of M¹ _(m)M² _((1−m))AX¹ _((2m+t))X² _((3−2m−t)), m is decreased with a longer deposition time, t is decreased with a longer deposition time, 1≧m≧0, and 1≧t≧0; wherein each of M¹ and M² is independently a divalent cation of Ge, Sn, or Pb, wherein A is a monovalent cation of methylammonium, ethylammonium, or formamidinium, wherein each of X¹ and X² is independently a monovalent anion of halogen, wherein M¹ has a lower atomic number than M², X¹ has a higher atomic number than X², or a combination thereof.
 5. The method as claimed in claim 4, wherein the first deposition source, the second deposition source, and the third deposition source comprise sputtering source or evaporation source.
 6. The method as claimed in claim 4, further comprising depositing a second conversion layer between the first conversion layer and the first electrode, wherein the second conversion layer is a composition-gradient perovskite, a part of the second conversion layer adjacent to the first electrode has an energy gap higher than that of a part of the second conversion layer adjacent to the first conversion layer, a part of the second conversion layer adjacent to the first conversion layer has an energy gap equal to that of a part of the first conversion layer adjacent to the second conversion layer, and a part of the second conversion layer adjacent to the first electrode has an energy gap lower than that of a part of the first conversion layer adjacent to the second electrode, wherein the step of depositing the second conversion layer comprises: providing m′ parts by mole of M³X³ ₂ by a fourth deposition source, providing 1−m′ parts by mole of M⁴X⁴ ₂ by a fifth deposition source, and providing a fixed amount of AX³ _(e)X⁴ _((1−t′)) by a sixth deposition source to deposit the second conversion layer on the first electrode, wherein the second conversion layer has a composition of M³ _(m′)M⁴ _((1−m′))AX³ _((2m′+t′))X⁴ _((3−2m′−t′)), m is decreased with a longer deposition time, t is decreased with a longer deposition time, 1≧m′≧0, and 1≧t′≧0; wherein each of M³ and M⁴ is independently a divalent cation of Ge, Sn, or Pb, wherein A is a monovalent cation of methylammonium, ethylammonium, or formamidinium, wherein each of X³ and X⁴ is independently a monovalent anion of halogen, wherein M³ has a higher atomic number than M⁴, X³ has a lower atomic number than X⁴, or a combination thereof.
 7. The method as claimed in claim 6, wherein the fourth deposition source, the fifth deposition source, and the sixth deposition source comprise sputtering source or evaporation source.
 8. A method of manufacturing a solar cell, comprising: providing m parts by mole of M¹X¹ ₂ by a first deposition source and providing 1−m parts by mole of M²X² ₂ by a second deposition source to deposit a M¹ _(m)M² _((1−m))X¹ _(2m)X² _((2−2m)) layer on a first electrode; providing AX¹ or AX² by a third deposition source, such that AX¹ or AX² reacts with the M¹ _(m)M² _((1−m))X¹ _(2m)X² _((2−2m)) layer to form a first conversion layer on the first electrode, wherein the first conversion layer is a composition-gradient perovskite of M¹ _(m)M² _((1−m))AX¹ _((2m+1))X² _((2−2m)) or M¹ _(m)M² _((1−m))AX¹ _((2m))X² _((3−2m)); and forming a second electrode on the first conversion layer, wherein a part of the first conversion layer adjacent to the first electrode has an energy gap lower than that of a part of the first conversion layer adjacent to the second electrode, wherein m is decreased with a longer deposition time and 1≧m≧0; wherein each of M¹ and M² is independently a divalent cation of Ge, Sn, or Pb, wherein A is a monovalent cation of methylammonium, ethylammonium, or formamidinium, wherein each of X¹ and X² is independently a monovalent anion of halogen, wherein M¹ has a lower atomic number than M², X¹ has a higher atomic number than X², or a combination thereof.
 9. The method as claimed in claim 8, wherein the first deposition source, the second deposition source, and the third deposition source comprise sputtering source or evaporation source.
 10. The method as claimed in claim 8, further comprising depositing a second conversion layer between the first conversion layer and the first electrode, wherein the second conversion layer is a composition-gradient perovskite, a part of the second conversion layer adjacent to the first electrode has an energy gap higher than that of a part of the second conversion layer adjacent to the first conversion layer, a part of the second conversion layer adjacent to the first conversion layer has an energy gap equal to that of a part of the first conversion layer adjacent to the second conversion layer, and a part of the second conversion layer adjacent to the first electrode has an energy gap lower than that of a part of the first conversion layer adjacent to the second electrode, wherein the step of depositing the second conversion layer comprises: providing m′ parts by mole of M³X³ ₂ by a fourth deposition source and providing 1−m′ parts by mole of M⁴X⁴ ₂ by a fifth deposition source to deposit a M³ _(m′)M⁴ _((1−m′))X³ _(2m′)X⁴ _((2−2m′)) layer on the first electrode; and providing AX³ or AX⁴ by a sixth deposition source, such that AX³ or AX⁴ reacts with the M³ _(m′)M⁴ _((1−m′))X³ _(2m′)X⁴ _((2−2m′)) layer to form a second conversion layer on the first electrode, wherein the second conversion layer is a composition-gradient perovskite of M³ _(m′)M⁴ _((1−m′))AX³ _((2m′+1))X⁴ _((2−2m′)) or M³ _(m′)M⁴ _((1−m′))AX³ _((2m′+1))X⁴ _((3−2m′)); wherein m′ is decreased with a longer deposition time and 1≧m′≧0; wherein each of M³ and M⁴ is independently a divalent cation of Ge, Sn, or Pb, wherein A is a monovalent cation of methylammonium, ethylammonium, or formamidinium, wherein each of X³ and X⁴ is independently a monovalent anion of halogen, wherein M³ has a higher atomic number than M⁴, X³ has a lower atomic number than X⁴, or a combination thereof.
 11. The method as claimed in claim 10, wherein the fourth deposition source, the fifth deposition source, and the sixth deposition source comprise sputtering source or evaporation source. 